Continuous process for producing alkylaluminum compounds

ABSTRACT

AN ALKYLALUMINUM COMPOUND IS PRODUCED CONTINOUSLY AND ECONOMICALLY WITH LESS ALUMINUM LOSS BY REACTING HYDROGEN AND AN ALKYLALUMINUM COMPOUND OR FURTHER AN OLEFIN IN ADDITION THERETO, WITH AN ALLOY CONTAINING ALUMINUM AND SILICON AND HAVING A SIZE LARGER THAN THAT OF A METAL RESIDUE TO BE WITHDRAWN OUT OF A REACTION SYSTEM IN A COLUMN-TYPE REACTOR THROUGH PASSAGE OF SAID HYDROGEN, ALKYLALUMINUM COMPOUND AND THE OLEFIN, IF NECESSARY THROUGH THE RECATOR PACKED WITH THE ALLOY FROM THE BOTTOM UPWARDS AT A TEMPERATURE OF 50*-200*C. UNDER A PRESSURE OF 10-300KG/CM2, WITHDRAWING A METAL RESIDUE MADE TO PASS SUBSTANTIALLY THROUGH 32-100 MESH SIZES BY THE REACTION OUT OF THE REACTION SYSTEM TOGETHER WITH THE ALKYLALUMINUM COMPOUND AND SEPARATING THE ALKYLALUMINUM COMPOUND FROM THE METAL RESIDUE.

15, 1974 EIICHI ICHIKI L CONTINUOUS PROCESS FOR PRODUCING ALKYLALUMINUMCOMPOUNDS Filed Feb, 16, 1971 United States Patent 3,786,080 CONTINUOUSPROCESS FOR PRODUCING ALKYLALUMINUM COMPOUNDS Eiichi Ichiki, Kazuo Iida,Atsuro Matsui, and Hidekimi Kadokura, Niihama-shi, Japan, assignors toSumitomo Chemical Company, Limited, Osaka, Japan Filed Feb. 16, 1971,Ser. No. 115,476 Claims priority, application Japan, Feb. 19, 1970, 45/14,586 Int. Cl. C07f /06 US. Cl. 260-448 A 13 Claims ABSTRACT OF THEDISCLOSURE An alkylaluminum compound is produced continuously andeconomically with less aluminum loss by reacting hydrogen and analkylaluminum compound or further an olefin in addition thereto, with analloy containing aluminu-m and silicon and having a size larger thanthat of a metal residue to be withdrawn out of a reaction system in acolumn-type reactor through passage of said hydrogen, alkylaluminumcompound and the olefin, if necessary, through the recator packed withthe alloy from the bottom upwards at a temperature of 50200 C. under apressure of 10400 kg./cm. withdrawing a metal residue made to passsubstantially through 32-100 mesh sizes by the reaction out of thereaction system together with the alkylaluminum compound and separatingthe alkylaluminum compound from the metal residue.

This invention relates to a continuous process for producing analkylaluminum compound by subjecting hydrogen and an alkylaluminumcompound, or hydrogen, an alkylalurninum compound and an olefin toreaction with an alloy containing aluminum and silicon.

A process for directly synthesizing an alkylaluminum compound bysubjecting metallic aluminum, hydrogen and an alkylaluminu'm compound orfurther an olefin in addition thereto to a reaction is well known fromlap taining aluminum and silicon, there are problems peculiar to thenature of the alloy as the raw material.

That is to say, when the alkylaluminum compound is continuously producedfrom an alloy containing aluminum and silicon, the metal that does nottake part in the reaction must be continuously withdrawn from thereaction system. However, when such metal is withdrawn therefrom at anearlier stage, the alloy containing a large amount of unreacted aluminummust be taken out together, and an aluminum loss is inevitable. On theother hand, when the reaction is carried out under such a condition thatthe aluminum contained in the alloy completely undergoes reaction, themetal that does not take part in the reaction is accumulated in thereaction system, and the desired continuous process cannot be carriedout. These are the problems encountered when the alloy is used as theraw material.

As a result of various studies on a continuous process for smoothly andefiiciently producing an alkylaluminum compound from an alloy containingaluminum and silicon, the present inventors have found unexpectedly aspecific relation between the particle size distribution and particlesizes of a metal residue as the reaction residue, and the aluminumcontent of the metal residue, irrespective of the sizes of the rawmaterial alloy, when an alloy incapable of passing through 100 mesh size(the term mesh herein used refers to Tyler standard screen series) isused as the raw material alloy. For example, the results as shown inTables 1 and 2 were obtained under the following conditions:

Composition of raw material alloy: 65.5% by weight of aluminum and 34.5%by weight of silicon Particle sizes of raw material alloy: 3-4 meshsizes Activation: 100 g. of said alloy was placed in 200 g. oftriisobutylaluminum containing 2 g. of ethoxysodium and activated at 150C. for 2 hours Synthesis: 400 g. of triisobutylaluminum, 880 g. ofisobutylene and 100 g. of said activated alloy were charged into anautoclave, and the content was heated anese Pat. No. 236,648. 49 to 130C. Then, the system was subjected to a pressure In said prior artprocess, the present inventors previof 100 kg./cm. with hydrogen and thereaction was ously found that the rate of reaction could be acceleratedcarried out with stirring. The reaction was discontinued by using analuminum alloy containing silicon in place at a definite time and thecontent was recovered. The of the metallic aluminum, rather than whenthe metallic particle size distribution of the metal residue and thealuminum was used alone. However, as is well known, a aluminum contentof the particles were measured.

TABLE 1 Extraction percentage (percent by weight) 1 Al content Alcontent Al content Amount (percent Amount (percent Amount. (percentParticle size of residue by of residue by of residue by (mesh size) (g.)weight) 2 (g.) we1ght) 2 (g welght) I 1 Extraction percentage (percentby weight) Amount of aluminum consumed in reaction (g.) Total aluminumamount in charged alloy (g.)

2 Al content (percent by weight) Total aluminum amount in eachdistribution (g.) Total amount of residue in each distribution (g.)

Another synthesis was carried out in the same manner as above, exceptthat an alloy having 12-14 mesh sizes was used as the raw material.

TABLE 2 Extraction percentage (percent by weight) 1 Particle Amount AlAmount Al Amount A1 size of content of content of content (mesh residue(percentby residue (percent by residue (percent by size) (g.) weight)(g.) weight) 1 (g.) weight) 18.5 65.4 9.9 63.1 1.8 63.5 43. a s4. 2 31.162.5 18.7 61.7 2.2 42.5 3.6 37.5 3.8 38.8 1. 22. 3 1. 4 17. 3 1. 9 15. 31.2 8.6 1.1 6.3 1.6 5.9 2.1 5.7 2.6 4.9 3.2 4.5 7. 4.6 12. 3 4. 3 19. 44. a

1 Same as footnote 1, see Table 1 above.

3 Same as footnote 2, see Table 1 above.

As is clear from the foregoing results that it has been cannot becarried out continuously. On the other hand, confirmed that theparticles of the raw material alloy when the metal residue incapable ofpassing through 32 containing aluminum and silicon were disintegratedmesh size is withdrawn out of the reaction system, the through thereaction; only a very small amount of alumimetal residue containing alarge amount of unreacted num was retained in the particles which weremade to aluminum is withdrawn out of the reaction system. Such passthrough 100 mesh size; the amount of particles havis not preferable. inglarger particle sizes was reduced with the progress Granules of the rawmaterial alloy are generally preof the reaction, whereas the amount ofthe particles pared by a lathe, shaper, drilling machine or throughcapable of passing through the 100 mesh size was incrushing, cutting,atomizing, etc. creased; the amount of the particles having intermedi-It is not always necessary but desirable to activate the ate particlesizes ranging from 32 to 100 mesh sizes was alloy containing aluminumand silicon when subjected to small and substantially unchanged. Thepresent inventors the reaction. Any of the well-known mechanical andhave established a continuous process for producing an chemicalactivation methods proposed for the aluminum alkylaluminum compoundwithout any substantial loss can be applied for activation of the rawmaterial alloy. of aluminum on the basis of said finding. For example, achemical activation method based on a That is, an object of the presentinvention is to protreatment with such a metallic compound as anactivating vide a continuous process for producing an alkylalumiagent asaluminum hydride, sodium hydride, diethylaluminum compound from an alloycontaining aluminum and num chloride, diisobutylaluminum chloride,triethylalumisilicon, which comprises reacting hydrogen and an alkyl- 35num, triisobutylaluminum, ethoxysodium, triisobutoxyaluminum compound orfurther an olefin in addition aluminum, etc. can be advantageously used.Furtherthereto with an alloy containing aluminum and silicon more, thealloy containing aluminum and silicon as the having larger sizes andshapes than those of metal residue raw material can be activated inadvance in another withdrawn from a reaction system, withdrawing a metalvessel and then charged to reactor, or activated in the residue made topass through 32-100 mesh sizes by the reactor. reaction together withthe alkylaluminum compound from In carrying out the present invention,the raw matethe reaction system and separating the alkylaluminum rialalloy containing aluminum and silicon is supplied compound from themetal residue. into a column-type reactor from the upper part of the Thepresent invention is carried out in a column-type reactor, and thereaction is carried out in a packed state reactor. in the column-typereactor.

The alloy containing aluminum and silicon used in the It is desirable tointermittently add the alloy containpresent invention is definedgenerally as an alloy coning aluminum and silicon into the reactor fromthe upper taining 87-30% by weight of aluminum, 13-70% by part of thereactor, in view of the amount of alloy weight of silicon, and 020% byweight of iron, copper, present in the reactor, after the reaction hasbeen started. titanium, magnesium, etc. in total. When the silicon con-The alkylaluminum compound used in the present intent is less than 13%by weight, the rate of rea tion vention includes such alkylaluminumcompounds having becomes lower, whereas when the amounts of silicon analkyl group having 2 to 20 carbon atoms as trialkyl and other metals areincreased, the amount of the matealuminum, dialkylahlminllm hydride(which is used in rials treated in the reaction operation becomeslarger. e prese ce of an olefin), alkylaluminum halide and That is, suchis economically undesirable. alkylaluminum alkoxide. These compounds areused alone Therefore, an alloy having 80-40% by weight of rin amiXtllrc. aluminum, 20-60% by weight of silicon and 020% by The olefinused in the present invention includes such weight of other metals intotal is preferably used. The Olefins having carbon atoms as ethylene,propylene, size of the alloy containing aluminum and silicon usediS0buty1ene,butene-l, butene-Z, pentene-l, hexene-l, hepas the rawmaterial must be larger than that of the metal Octane-1,2-ethylhfixene-l, residue withdrawn from the reaction system. Forexample, The alkylaluminum compound, hydrogen and the Olefi when themetal residue to be withdrawn from the reacare introduced into the yp rr m th tion system is capable of passing through the 100 mesh lower partof the reactor. Of course, a portion of said size, an alloy as the rawmaterial incapable of passing raw materials can be introduced into thereactor from a through 100 mesh size, preferably 60 mesh size is used.middle Position of the t When the metal residue to be withdrawn from thereac- The introduction of the alkylaluminum compound, ytion system iscapable of passing through the 32 mesh dfogen and the Olefin into t e ractor from the lower size, an alloy incapable of passing through 32 meshsize, P thereof is an important condition Carrying out preferably 14mesh size, is used The foregoing explathe present iIlVEIltlOl'l in thatthe metal residue made to nation is made only of the upper and lowerlimbs, but a pass through 32-100 mesh sizes by the reaction is to besimilar thing is applicable to the mesh sizes intermediate Withdrawn outof the reaction y between these upper and lower limits, The reactiontemperature is 50-200 C., particularly When a raw material alloy capableof passing through 100-150 C. in the present invention. When thereaction a 100 mesh size is used, separation of the raw materialtemperature is less than 50 C., the rate of reaction be alloy and theresidue becomes difiicult, and the reaction comes lower, and thereaction becomes industrially disadvantageous. Further, the temperatureabove 200 C. is not preferable, because the alkylaluminum compoundundergoes decomposition.

The reaction pressure is 10300 kg/cm. in the present invention. When thereaction pressure is less than kg./cm. the rate of reaction becomeslower, whereas if the reaction pressure exceeds 300 kg./cm. theapparatus becomes complicated and impractical.

The reaction is carried out under said synthesis conditions, and themetal residue made to pass through 32-100 mesh sizes by the reaction iswithdrawn out of the reaction system together with the alkylaluminumcompound.

The metal residue made to pass through the 32-100 mesh sizes isseparated from the upper part of the reactor in the following manner.The metal residue can overflow at the upper part of the reactor byadjusting the supply of the alkylaluminum compound and hydrogen, or a32-100 mesh sizes wiremesh or a bafiie plate or other means is providedat the upper part of the reactor to make the metal residue passtherethrough or thereover. Such means is only selected properly at theactual practice.

The separation of the metal residue capable of passing through 32-100mesh sizes is a very important condition for carrying out the reactionsmoothly and efliciently without retaining the metal residue containingsubstantially no remaining aluminum component unnecessarily in thereactor, as is clear from said experimental facts.

After the metal residue capable of passing through the 32-100 mesh sizeshas been withdrawn from the reaction system, the alkylaluminum compoundis separated from the metal residue capable of passing through the32-100 mesh sizes. The separation can be carried out by anyone offiltration, centrifugal separation, sedimentation, evaporation, etc. Itis preferable in an industrial practice to recycle a portion of theproduct alkylaluminum compound obtained by the separation as the rawmaterial.

As explained above, the present invention has the following considerablyremarkable effects:

(1) Since the reaction is carried out in a column-type reactor in aclosely packed state of the raw material alloy, the side reactionoccurring in the liquid phase section, that is, hydrogenation reactionand dimerization reaction of olefin, can be relatively prevented.

(2) Since the raw material alloy having relatively larger particle sizesis used, a cost for the pulverization, crushing, etc. becomes lower.

(3) 'By withdrawing the metal residue capable of passing through 32-100mesh sizes from the reaction system, the aluminum loss is eliminated andthe metal residue that does not take part in the reaction can besmoothly withdrawn from the reaction system.

According to the present invention, an alkylaluminum compound can beproduced smoothly and etficiently in a continuous manner from an alloycontaining aluminum and silicon.

Now, the present invention will be explained, referring to examples anddrawing, but will not be restricted to the examples, which are only toillustrate the embodiments of the present invention and do not restrictthe scope of the present invention.

FIG. 1 shows a schematic fiow diagram showing an example of a reactorused in carrying out the present invention and streams of reactingmaterials and a product in the reaction system.

EXAMPLE 1 Into a reactor 10 having an inner diameter of 85 mm. and aheight of 3 m. provided with a wiremesh having 32 mesh size at the upperpart of the. reactor as shown in FIG. 1 was packed 15.0 kg. of apreviously activated alloy consisting of 65.5% by weight of aluminum and34.5% by weight of silicon and having particle sizes of 3-4 mesh. 27.3kg./hour of triethylaluminum and 18 Nm. /hour of hydrogen were suppliedthrough a conduit 2 and conduit 3, respectively, and the reaction wascarried out at a reaction temperature of 130 C. under a reactionpressure of 75 kg./cm. With the progress of the reaction, 5.0 kg. of thepreviously activated raw material alloy was supplied to the reactorthrough a hopper 1 at the upper part of the reactor at an interval of 3hours 20 minutes. A reaction product solution containing hydrogen and ametal residue capable of passing through 32 mesh size was withdrawn froma conduit 4 and led to a solid-liquid separator 11, where the gas wasvented from an outlet 7, and then the metal residue was discharged froman outlet 5. On the other hand, diethylaluminum hydride, a reactionproduct solution withdrawn from an outlet 6, was passed through anolefin-addition reactor, not shown in the drawing, to convert it totriethylaluminum, and then recycled to the reactor 10 as the rawmaterial from the conduit 2 through a conduit 8, and a portion thereofwas withdrawn from the conduit 6. When the reaction was brought into astationary state, the reaction product solution from the reactorcontained 19.4 kg/hour of triethylaluminum, 8.9 kg./hour ofdiethylaluminum hydride and 570 g./hour of the metal residue capable ofpassing through 32 mesh size. Analysis of the metal residue revealedthat 570 g. of the metal residue contained 52 g. of aluminum.

For comparison, the reaction was carried out in the same manner as aboveexcept that the wiremesh was replaced with a 14 mesh size wiremesh towithdraw a metal residue capable of passing through 14 mesh size. As aresult, the reaction product solution contained 21.3 kg./ hour oftriethylaluminum, 6.8 kg./hour of dicthyl-aluminum hydride and 793g./hour of the metal residue capable of passing through 14 mesh size.Analysis of the metal residue revealed that 793 g. of the metal residuecontained 275 g. of aluminum.

As is clear from the above result, when the metal residue capable ofpassing through 14 mesh size was withdrawn out of the reaction system,the aluminum loss was very great, and considerably uneconomical, ascompared with the present invention.

EXAMPLE 2 Into the same reactor 10 as in Example 1 except that thewiremesh 20 was removed from the reactor was packed 15.0 kg. of apreviously activated alloy consisting of 73.3% by weight of aluminum and26.7% by weight of silicon and having particle sizes of 6l0 mesh. 7.9kg./hour of triisobutylaluminum was introduced into the reactor throughthe conduit 2, and 11.2 kg./hour of isobutylene and 6.0 Nrnfi/hour ofhydrogen were introduced into the reactor through the conduit 3, and thereaction was carried out at a reaction temperature of 130 C. under areaction pressure of kg./cm. With the progress of the reaction, 5.4 kg.of the previously activated raw material alloy was supplied to thereactor from the hopper 1 at the upper part of the reactor at aninterval of 4 hours.

'A reaction product solution containing a metal residue capable ofpassing through 60 mesh size was withdrawn from the reactor 10, and thenled to the solid-liquid separator 11, where the gas was vented from theoutlet 7, and the metal residue was discharged from the outlet 5. On theother hand, a portion of triisobutylaluminum, the reaction productsolution withdrawn from the conduit 6, was recycled to the reaction asthe raw material from the conduit 2 through the conduit. 8. When thereaction was brought into a stationary state, the reaction productsolution from the reactor contained 14.9 kg./ hour oftriisobutylaluminum, and 406 g./hour of the metal residue capable ofpassing through 60 mesh size.

Analysis of the metal residue revealed that 406 g. of the metal residuecontained 46 g. of aluminum.

The reaction could be continuously carried out without any trouble.

7 EXAMPLE 3 Crude alloy prepared by direct reduction of a mixture ofclay and bauxite (the alloy composition was 58.4% by weight of aluminum,39.0% by weight of silicon, 2.1% by weight of iron and 0.5% by weight oftitanium) was crushed by a crusher, whereby a raw material alloy having22.5% by Weight of 3-4 mesh size component, 41.7% by weight of 4-8 meshsize component, 26.5% by weight of 8-14 mesh size component, 6.9% byweight of 14-32 mesh size component and 2.4% by weight of 32 mesh sizethrough component was obtained.

Into the same reactor as in Example 2 was packed 15.0 kg. of said alloypreviously activated, and 7.9 kg./hour of triisobutylaluminum wasintroduced into the reactor through the conduit 2, and 11.2 kg./hour ofisobutylene and 6.0 Nm. /hour of hydrogen were introduced thereinthrough the conduit 3. The reaction was carried out at a reactiontemperature of 130 C. under a reaction pressure of 100 kg./cm. With theprogress of the reaction, 4.8 kg. of the previously activated rawmaterial alloy was supplied to the reactor from the hopper 1 at theupper part of the reactor at an interval of 4 hours.

A reaction product solution containing a metal residue capable ofpassing through 60 mesh size was withdrawn from the reactor and then ledto the solid-liquid separator 11, where the gas was vented from theoutlet 7, and the metal residue was discharged from the outlet '5. Onthe other hand, a portion of triisobutylaluminum, the reaction productsolution withdrawn from the conduit 6, was recycled to the reactor asthe raw material from the conduit 2 through the conduit 8. When thereaction was brought into a stationary state, the reaction productsolution from the reactor contained 12.7 kg./hour of triisobutylaluminumand 546 g./hour of the metal residue capable of passing through the 60mesh size.

Analysis of the metal residue revealed that 546 g. of the metal residuecontained 47 g. of aluminum.

The reaction could be continuously carried out without any trouble atall.

What is claimed is:

1. A continuous process for producing an alkylaluminum compound byreacting hydrogen and an alkylaluminum compound selected from the groupconsisting of trialkyl aluminum, dialkylalumiuum hydride, alkylaluminumhalide and alkylaluminium alkoxide with or without an olefin with analloy containing aluminum and silicon in particle form at an elevatedtemperature and elevated pressure, which comprises continuouslywithdrawing the smaller particles of below about 100 mesh being formedduring the reaction and essentially consisting of those aly componentswhich do not react with the alkylaluminum compound from the reactortogether with the alkylaluminum compound, and then separating thealkylaluminum compound from the metal residue.

2. A continuous process according to claim 1, wherein the reaction iscarried out in a column-type reactor.

3. A continuous process according to claim 1 wherein the startingaluminum-silicon alloys having a particle size of above 32 mesh is used.

4. A continuous process according to claim 2, wherein the reaction iscarried out by supplying an alkylaluminum compound and hydrogen orfurther an olefin in addition thereto to the lower part of thecolumn-type reactor packed with the alloy and withdrawing the metalresidue together with the alkylaluminum from the upper part of thereactor, while supplying the alloy to the reactor intermittently.

5. A continuous process according to claim 1, wherein the reaction iscarried out at a temperature of 50 -200 C.

6. A continuous process according to claim 5, wherein the reaction iscarried out at a temperature of C.

7. A continuous process according to claim 1, wherein the reaction iscarried out under a pressure of 10-300 kg./cm.

8. A process according to claim 1, wherein the previously activatedalloy is used.

9. A process according to claim 1, wherein the alloy containing 80-40%by weight of aluminum, 20-60% by weight of silicon and 0-20% by weightof other metals in total is used.

10. A process according to claim 1, wherein the alkylaluminum isalkylaluminum compounds having an alkyl group having 2 to 20 carbonatoms.

11. A process according to claim 10, wherein the alkylaluminum compoundis trialkylalurninum, dialkylaluminum hydride, alkylaluminium halide andalkylaluminurn alkoxide.

12. A process according to claim 1, wherein the olefin is olefins having2-20 carbon atoms.

13. A process according to claim 12, wherein the olefin is ethylene,propylene, isobutylene, butene-l, butene-Z, pentene-l, hexene-l,heptene-l, octene-l and 2-ethylhexane-1.

References Cited UNITED STATES PATENTS 2,930,808 3/1960 Lasel 260448 A3,393,217 7/1968 Ichiki et al 260448 A 3,402,190 9/1968 Toyoshima et al.260448 A 3,388,142 6/1968 Cameron et al. 260448 A 3,207,770 9/ 1965Ziegler et al. 260448 A 3,373,179 3/1968 Lewis 260448 A v FOREIGNPATENTS 787,945 6/ 1968 Canada 260448 A 1,167,837 4/1958 Germany 260448A HELEN M. S. SNEED, Primary Examiner

